JPH06271786A - Phthalocyanine composition, its preparation, and electrophotographic photoreceptor and coating fluid for charge generating layer which are made by using the same - Google Patents

Abstract

PURPOSE:To obtain a phthalocyanine composition excellent in charge build-up characteristics, dark decay, and sensitivity. CONSTITUTION:To produce a phthalocyanine composition having main diffraction peaks at Bragg angles (2theta+ or -0.2 deg.) of 7.5 deg., 24.2 deg. and 27.3 deg. in the X-ray diffraction spectrum by using Cu Kalpha radiation, a phthalocyanine mixture containing titanylphthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is precipitated in water by the acid pasting method to give a precipitate having a characteristic diffraction peak at a Bragg angle (2theta+ or -0.2 deg.) of 27.2 deg. in the X-ray diffraction spectrum by using Cu Kalpha radiation, and this precipitate is treated with a mixture of an aromatic organic solvent and water. This composition is used to produce an electrophotographic photoreceptor and a coating fluid for a charge generating layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phthalocyanine composition having high sensitivity, a method for producing the same, an electrophotographic photoreceptor using the same and a coating solution for a charge generating layer.

[0002]

2. Description of the Related Art As a conventional electrophotographic photosensitive member, selenium (S) of about 50 μm is formed on a conductive substrate such as aluminum.
e) There is a film formed by a vacuum evaporation method. However, this Se photoconductor has a problem that it has sensitivity only up to a wavelength of about 500 nm. Moreover, a Se layer of about 50 μm is formed on the conductive substrate, and further several μm is formed on this.
There is a photoconductor on which a selenium-tellurium (Se-Te) alloy layer is formed. This photoconductor has a higher Te content in the Se-Te alloy, but the spectral sensitivity extends to a longer wavelength,
As the amount of Te added increases, the surface charge retention property becomes poor, and there is a serious problem that it cannot be used as a photoconductor in practice.

A charge generating layer is formed by coating a chlorocyan blue or squarylium acid derivative of about 1 μm on an aluminum substrate, and a mixture of a polyvinylcarbazole or pyrazoline derivative having a high insulation resistance and a polycarbonate resin is formed on the charge generating layer. There is a so-called composite two-layer type photoconductor in which a charge transport layer is formed by coating 10 to 20 μm, but in reality, this photoconductor does not have sensitivity to light of 700 nm or more.

In recent years, in this composite two-layer type photoreceptor,
The above drawbacks have been improved, that is, the semiconductor laser oscillation region 80.
Although many photoreceptors having a sensitivity of around 0 nm have been reported, most of them use a phthalocyanine pigment as a charge generating material, and polyvinylcarbazole, which has a thickness of about 0.5 to 1 μm, is formed on the charge generating layer. A mixture of a pyrazoline derivative or a hydrazone derivative and a polycarbonate resin or a polyester resin having a high insulation resistance is used in an amount of 10 to 2
A coating of 0 μm is formed to form a charge transport layer to form a composite two-layer type photoreceptor.

Phthalocyanines differ not only in their absorption spectra and photoconductivity depending on the type of central metal, but also in their physical properties depending on the crystal type. Even with phthalocyanines of the same central metal, there are specific crystal types. Several examples have been reported that have been selected for electrophotographic photoreceptors.

For example, titanyl phthalocyanine has various crystal forms, and it has been reported that there are large differences in chargeability, dark decay, sensitivity, etc. due to the difference in the crystal forms.

Japanese Patent Application Laid-Open No. 59-49544 discloses that the crystal form of titanyl phthalocyanine is Bragg angle (2
θ ± 0.2 degrees) of 9.2 degrees, 13.1 degrees, 20.7 degrees,
It is shown that those giving a strong diffraction peak at 26.2 degrees and 27.1 degrees are preferable, and an X-ray diffraction spectrum diagram is shown. The electrophotographic characteristics of the photoreceptor using this crystalline form of titanyl phthalocyanine as a charge generating material are as follows: dark decay (DDR): 85%, sensitivity (E _1/2 ): 0.
It is 57 lux · sec.

Further, in JP-A-59-166959, a vapor-deposited film of titanyl phthalocyanine is allowed to stand in saturated steam of tetrahydrofuran for 1 to 24 hours to change its crystal form to form a charge generation layer. The X-ray diffraction spectrum has a small number of peaks and a wide width, and Bragg angles (2θ ± 0.2 degrees) of 7.5 degrees, 12.6 degrees, and 13.0 degrees.
It has been shown to give strong diffraction peaks at degrees, 25.4 degrees, 26.2 degrees and 28.6 degrees. The electrophotographic characteristics of the photoconductor using this crystalline form of titanyl phthalocyanine as a charge generating material are dark decay (DDR): 86% and sensitivity (E _1/2 ): 0.7 lux · sec.

In Japanese Patent Application Laid-Open No. 2-198452, the crystal form of titanyl phthalocyanine is described as Bragg angle (2
High sensitivity (1.7 mJ / m ² ) has a main diffraction peak at 27.3 degrees (θ ± 0.2 degrees), and its production method is 60 ° C. 1 in a mixture of water and ortho-dichlorobenzene.
It is shown to heat and stir for hours.

Japanese Unexamined Patent Publication (Kokai) No. 2-256059 describes a black angle (2θ) as a crystal form of titanyl phthalocyanine.
Those having a main diffraction peak at 27.3 degrees (± 0.2 degrees) have high sensitivity (0.62 lux · sec), and as a manufacturing method thereof, stirring in 1,2-dichloroethane at room temperature is possible. It is shown.

As described above, the phthalocyanines have greatly different electrophotographic characteristics depending on the crystal form, and the crystal form is an important factor affecting the performance as an electrophotographic photoreceptor.

Japanese Unexamined Patent Publication (Kokai) No. 62-194257 discloses 2
Examples of using a mixture of two or more phthalocyanines, for example,
It has been shown to use a mixture of titanyl phthalocyanine and metal-free phthalocyanine as a charge generating material.

As described above, titanyl phthalocyanine has extremely high sensitivity due to the crystal form conversion and exhibits excellent characteristics. However, in the application such as laser printer,
Higher image quality and higher definition have been advanced, and there is a demand for an electrophotographic photoreceptor having higher sensitivity.

[0014]

DISCLOSURE OF THE INVENTION The present invention provides a phthalocyanine composition having high sensitivity, a method for producing the same, an electrophotographic photoreceptor using the same and a coating liquid for a charge generating layer.

[0015]

The present invention relates to CuKα X
In the line diffraction spectrum, the Bragg angle (2θ ± 0.2
Phthalocyanine composition having major diffraction peaks at 7.5 degrees, 24.2 degrees and 27.3 degrees.

In the present invention, a phthalocyanine mixture containing titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is precipitated in water by the acid pasting method, and the Bragg angle (2θ ± 2θ) in the X-ray diffraction spectrum of CuKα. 0.2 °) 27.2 ° A precipitate having a characteristic diffraction peak is obtained, and the precipitate is subsequently treated with an aromatic organic solvent-water mixed solvent. In the X-ray diffraction spectrum, the Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 24.
The present invention relates to a method for producing a phthalocyanine composition having major diffraction peaks at 2 degrees and 27.3 degrees.

The present invention also provides an electrophotographic photosensitive member having a photoconductive layer containing an organic photoconductive substance on a conductive substrate, wherein the organic photoconductive substance has a Bragg angle in an X-ray diffraction spectrum of CuKα. (2θ ± 0.2 degrees) 7.
The present invention relates to an electrophotographic photosensitive member which is a phthalocyanine composition having major diffraction peaks at 5 degrees, 24.2 degrees and 27.3 degrees.

The present invention also relates to a charge generation layer coating liquid containing the phthalocyanine composition obtained by the above-mentioned production method.

The present invention will be described in detail below.

Generally, a phthalocyanine mixture is a simple physical mixture of two or more phthalocyanines used as a raw material, and the X-ray diffraction pattern of the phthalocyanine mixture is a mixture of the individual phthalocyanine used as a raw material.
It consists of overlapping patterns. On the other hand, the phthalocyanine composition of the present invention is a mixture of the phthalocyanines used as raw materials at the molecular level, and the X-ray diffraction pattern is a combination of peak patterns of individual phthalocyanines used as raw materials. Shows a pattern different from.

The titanyl phthalocyanine used in the present invention can be produced, for example, as follows.

18.4 g (0.144 mol) of phthalonitrile are added to 120 ml of α-chloronaphthalene and then 4 ml (0.0364 mol) of titanium tetrachloride are added dropwise under a nitrogen atmosphere. After dripping, the temperature is raised and stirred with 200 to 220
After reacting at ℃ for 3 hours, hot filtration at 100 to 130 ℃, washed with α-chloronaphthalene, then methanol. Hydrolyze with 140 ml of deionized water (90 ℃, 1
Time), repeat this operation until the solution becomes neutral, and wash with methanol. Next, the substrate is thoroughly washed with NMP at 100 ° C., and then with methanol. The compound thus obtained is heated and dried at 60 ° C. under vacuum to obtain titanyl phthalocyanine (yield 46%).

In the present invention, the central metal used in the present invention is a trivalent metal halide phthalocyanine.
Examples of the valent metal include In, Ga and Al, and examples of the halogen include Cl and Br. The phthalocyanine ring may have a substituent such as a halogen. This compound is a known compound, and among them, for example, the synthesis method of monohalogenated metal phthalocyanine and monohalogenated metal halogen phthalocyanine is described in Inorganic Chemistry, 19 ,
3131 (1980) and JP-A-59-44054.

The monohalogenated metal phthalocyanine can be produced, for example, as follows. Phtharonitrile 78.2 mmol and metal trihalide 15.
8 mmol was added twice to 100 ml of quinoline deoxygenated and deoxygenated, heated under reflux for 0.5 to 3 hours and then gradually cooled, and then 0
After cooling to ℃, filtered and crystallized with methanol, toluene,
Then, after washing with acetone, it is dried at 110 ° C.

The monohalogenated metal halogen phthalocyanine can be produced as follows. 156 mmol of phthalonitrile and metal trihalide 3
7.5 mmol was mixed and melted at 300 ° C. and then heated for 0.5 to 3 hours to obtain a crude product of a monohalogenated metal halogen phthalocyanine, which was subjected to α-chloronaphthalene using a Soxhlet extractor. To wash.

In the present invention, the composition ratio of the phthalocyanine mixture containing a titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is such that the content ratio of the titanyl phthalocyanine is from the viewpoint of electrophotographic characteristics such as charging property, dark decay and sensitivity. It is preferably in the range of 20 to 95% by weight, more preferably in the range of 50 to 90% by weight, particularly preferably in the range of 65 to 90% by weight, 7
Most preferably, it is in the range of 5 to 90% by weight.

The phthalocyanine mixture is amorphized by being precipitated in water by the acid pasting method.
For example, 1 g of the phthalocyanine mixture is dissolved in 50 ml of concentrated sulfuric acid, stirred at room temperature, and then added to 1 liter of ion-exchanged water cooled with ice water for about 1 hour, preferably 40 minutes to 50 minutes.
Drop by minute to precipitate. After standing overnight, the supernatant is removed by decantation, and the precipitate is collected by centrifugation. Thereafter, the precipitate is repeatedly washed with ion-exchanged water as washing water until the pH after washing the washing water is 2 to 5, preferably around pH 3 and the conductivity is 5 to 500 μS / cm. Then, after thoroughly washing with methanol, vacuum heating and drying at 60 ° C. give a powder. The powder of the precipitate thus formed, which is composed of titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent, is CuK
In the X-ray diffraction spectrum of α, the Bragg angle (2θ ±
The peak is wide except for the clear diffraction peak at 27.2 degrees (0.2 degrees), and the value cannot be clearly defined. When the pH exceeds 5, the X-ray diffraction spectrum of CuKα has a black angle (2θ ± 0.2 degrees) of 27.2.
The characteristic peak intensity of the degree is reduced, and the new peak intensity is increased to 6.8 degrees.
A peak stronger than the peak intensity of 7.2 degrees was generated, and even if this powder was subjected to crystal conversion using a mixed solvent of an aromatic organic solvent and water, the Bragg angle (2θ ± 0. It is not possible to obtain a composition having a characteristic peak at 7.5 degrees, 24.2 degrees and 27.3 degrees (2 degrees), and a composition which does not have this characteristic peak has poor sensitivity. If the pH of the wash water after washing is less than 2 or more than 5, the chargeability, dark decay, sensitivity, etc. tend to be poor. In addition, the conductivity after washing with wash water is 5
If it is less than μS / cm or more than 500 μS / cm, the chargeability,
Dark decay and sensitivity tend to be poor.

The precipitate thus obtained is crystallized by treating with a mixed solvent of an aromatic organic solvent and water to obtain the phthalocyanine composition of the present invention. From the viewpoint of crystal conversion efficiency, the ratio of aromatic organic solvent and water used is 1/99 for the aromatic organic solvent / water (weight ratio).
To 99/1 is preferable, and 50/50 to 99 /
It is more preferably 1. Further, the amount of the precipitate with respect to water is preferably 1 to 50% by weight. This treatment can be performed by contacting the precipitate with a mixed solvent of an aromatic organic solvent and water at 20 ° C to 100 ° C for 1 hour or more. The contact method may be heating and stirring with a stirrer, or milling with a ball mill or the like. Examples of the aromatic organic solvent used in this treatment include benzene, toluene, xylene and the like.

The absorption spectrum of the phthalocyanine composition of the present invention has an absorption spectrum of 800 to 830 nm of 620.
From the viewpoint of sensitivity, it is preferable that the absorbance is larger than ˜660 nm.

The electrophotographic photoreceptor of the present invention comprises a photoconductive layer provided on a conductive support. In the present invention,
The photoconductive layer is a layer containing an organic photoconductive substance, such as a film of an organic photoconductive substance, a film containing an organic photoconductive substance and a binder, a composite type film consisting of a charge generation layer and a charge transport layer, and the like. is there.

As the organic photoconductive substance, the phthalocyanine composition is used as an essential component, and known substances can be used in combination. As the organic photoconductive substance, it is preferable to use a charge generating substance (organic pigment generating a charge) and / or a charge transporting substance in combination with the phthalocyanine composition. The charge generating layer contains the phthalocyanine composition and / or the charge generating substance (organic pigment that generates a charge), and the charge transporting layer contains the charge transporting substance.

Examples of the charge generating substance (organic pigment that generates a charge) include azoxybenzene type, disazo type, trisazo type, benzimidazole type, polycyclic quinone type, indigoid type, quinacridone type, perylene type, methine type,
Pigments known to generate electric charges such as metal-free or metal-type phthalocyanine-based pigments having various crystal structures such as α-type, β-type, γ-type, δ-type, ε-type, and χ-type can be used. These pigments are disclosed, for example, in JP-A-47-375.
43, JP-A 47-37544, JP-A 4
7-18543, JP-A-47-18544, JP-A-48-43942, JP-A-48-70.
538, JP 49-1231, and JP 4
9-105536, JP-A-50-75214, JP-A-53-44028, JP-A-54-17.
No. 732, etc. In addition, JP-A-58-
182640 and European Patent Publication No. 92,2
.Tau., .Tau. ', .Eta. And .eta.'
Type metal-free phthalocyanines can also be used. In addition to these substances, any organic application that generates a charge carrier upon irradiation with light can be used.

As the above-mentioned charge transporting substance, polymer compounds such as poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, polyvinylindroquinoxaline, polyvinylbenzothiophene, polyvinylanthracene and polyvinylacridine are used. , Polyvinylpyrazoline, etc., and low molecular compounds include fluorenone, fluorene, 2,7-dinitro-9-fluorenone, 4H-indeno (1,2,6)
Thiofen-4-one, 3,7-dinitro-dibenzothiophen-5-oxide, 1-bromopyrene, 2-phenylpyrene, carbazole, N-ethylcarbazole, 3-phenylcarbazole, 3- (N-methyl-N).
-Phenylhydrazone) methyl-9-ethylcarbazole, 2-phenylindole, 2-phenylnaphthalene, oxadiazole, 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole, 1-
Phenyl-3- (4-diethylaminostyryl) -5-
(4-Diethylaminostyryl) -5- (4-diethylaminophenyl) pyrazoline, 1-phenyl-3- (p
-Diethylaminophenyl) pyrazolin, p- (dimethylamino) -stilbene, 2- (4-dipropylaminophenyl) -4- (4-dimethylaminophenyl) -5
-(2-chlorophenyl) -1,3-oxazole, 2
-(4-Dimethylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2-fluorophenyl)-
1,3-oxazole, 2- (4-diethylaminophenyl) -4- (4-dimethylaminophenyl) -5-
(2-fluorophenyl) -1,3-oxazole, 2
-(4-Dipropylaminophenyl) -4- (4-dimethylaminophenyl) -5- (2-fluorophenyl)
Examples include -1,3-oxazole, imidazole, chrysene, tetraphene, aclidene, triphenylamine, benzidine, and their derivatives. As the charge transporting substance, a benzidine derivative is preferable, and among them, the compound represented by the general formula [I]

[Chemical 2] (R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ₃ are each independently a hydrogen atom. Or an alkyl group, Ar ₁ and Ar ₂ each independently represent an aryl group, and p, q, r and s each independently represent an integer of 0 to 5). preferable.
In the general formula [I], examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n group.
-Butyl group, tert-butyl group and the like can be mentioned. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group and the like. Examples of the aryl group include a phenyl group, a tolyl group, a biphenyl group, a terphenyl group and a naphthyl group. Examples of the fluoroalkyl group include a trifluoromethyl group, a trifluoroethyl group, a heptafluoropropyl group and the like.
Examples of the fluoroalkoxy group include trifluoromethoxy group, 2,3-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 1H, 1H-pentafluoropropoxy group, hexafluoro-iso-propoxy group, 1
H, 1H-pentafluorobutoxy group, 2, 2, 3,
4,4,4-hexafluorobutoxy group, 4,4,4-
Examples thereof include fluoroalkoxy groups such as trifluorobutoxy group. As the benzidine derivative represented by the general formula [I], specifically, the following No. 1-No. 6 and the like.

[0034]

[Chemical 3]

[Chemical 4]

When the above-mentioned phthalocyanine composition and a charge generating substance (organic pigment generating a charge) optionally used (both are the former) and a charge transporting substance (the latter is a mixture) are used ( In the case of forming a single-layer type photoconductive layer), it is preferable that the latter / the former be mixed in a weight ratio of 10/1 to 2/1. At this time, the binder is 0 to 500% by weight based on the total amount of these compounds (the former + the latter),
In particular, it is preferably used in the range of 30 to 500% by weight. When using these binders, a plasticizer,
Additives such as a fluidity imparting agent and a pinhole inhibitor can be added as necessary.

When a composite type photoconductive layer comprising a charge generating layer and a charge transporting layer is formed, the phthalocyanine composition and optionally a charge generating substance (organic pigment which generates a charge) are contained in the charge generating layer. The binder may be contained in an amount of 500% by weight or less based on the total amount of the phthalocyanine composition and the charge generating substance, and the above-mentioned additive may be added to the total amount of the phthalocyanine composition and the charge generating substance. Alternatively, it may be added in an amount of 5% by weight or less. Further, the charge transport layer may contain the above-mentioned charge transport material, and may further contain a binder in an amount of 500% by weight or less based on the charge transport material. When the charge transporting substance is a low molecular weight compound, it is preferable that the binder is contained in an amount of 50% by weight or more based on the compound.

Binders that can be used in all of the above cases include silicone resin, polyamide resin, polyurethane resin, polyester resin, epoxy resin, polyketone resin, polycarbonate resin, polyvinyl butyral resin, polyacrylic resin, polystyrene resin, melamine resin. , Styrene-butadiene copolymer, polymethylmethacrylate resin, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyacrylamide resin, polyvinylcarbazole, polyvinylpyrazoline, polyvinylpyrene, etc. Can be mentioned. Further, a thermosetting resin and a photocuring resin which are crosslinked by heat and / or light can also be used. In any case, there is no particular limitation as long as it is an insulating resin capable of forming a film in a normal state and a resin that is cured by heat and / or light to form a film.

Examples of the plasticizer as the additive include halogenated paraffin, dimethylnaphthalene, dibutyl phthalate, and the like, and as the fluidity-imparting agent, Modaflow (manufactured by Monsanto Chemical Co., Ltd.), Acronal 4F (manufactured by Buzzuf Co.), etc. As the pinhole inhibitor,
Examples thereof include benzoin and dimethyl phthalate. These may be appropriately selected and used, and the amount thereof may be appropriately determined.

In the present invention, the conductive substrate is a conductor such as paper or plastic film that has been subjected to a conductive treatment, a plastic film in which a metal foil such as aluminum is laminated, or a metal plate.

The electrophotographic photosensitive member of the present invention comprises a photoconductive layer formed on a conductive base material. The thickness of the photoconductive layer is preferably 5 to 50 μm. When the composite type of the charge generation layer and the charge transport layer is used as the photoconductive layer, the charge generation layer is preferably 0.001 to 10 μm, particularly preferably 0.2.
The thickness is about 5 μm. If it is less than 0.001 μm, it is difficult to uniformly form the charge generation layer, and if it exceeds 10 μm, the electrophotographic properties tend to deteriorate. The thickness of the charge transport layer is preferably 5 to 50 μm, particularly preferably 8
Is about 25 μm. If the thickness is less than 5 μm, the initial potential tends to be low, and if it exceeds 50 μm, the sensitivity tends to decrease.

To form a photoconductive layer on a conductive substrate, a method of depositing an organic photoconductive substance on the conductive substrate, an organic photoconductive substance and, if necessary, other components are added with toluene and xylene. Aromatic solvents such as methylene chloride, halogenated hydrocarbon solvents such as carbon tetrachloride, alcohol solvents such as methanol, ethanol and propanol, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, There is a method of uniformly dissolving or dispersing it in an ether solvent such as the above to form a coating material for the photoconductive layer, coating it on a conductive base material, and drying. As a coating method, a spin coating method, a dipping method or the like can be adopted.
When the charge generation layer and the charge transport layer are formed, the charge generation layer coating liquid and the charge transport layer coating liquid can be similarly prepared, and in this case, which of the charge generation layer and the charge transport layer is used? The charge generation layer may be an upper layer, and the charge generation layer may be sandwiched between two charge transport layers.

When the phthalocyanine composition of the present invention is applied by the spin coating method, the phthalocyanine composition and a binder used as necessary are dissolved in a solvent such as chloroform, toluene, tetrahydrofuran, 2-ethoxyethanol or the like to obtain a coating. Rotation speed 500 to 4 using liquid
Spin coating at 000 rpm is preferred,
Further, when applying by a dipping method, it is preferable to immerse the conductive substrate in a coating liquid in which the phthalocyanine composition and a binder used if necessary are dispersed in the above solvent using a ball mill, ultrasonic waves, or the like. .

The electrophotographic photosensitive member according to the present invention may further have a thin adhesive layer or a barrier layer directly on the conductive substrate, or may have a protective layer on the surface.

[0044]

EXAMPLES The present invention will be described in detail below with reference to production examples and examples of phthalocyanine compositions.

Production Example 1 1 g of a phthalocyanine mixture consisting of 0.75 g of titanyl phthalocyanine and 0.25 g of indium phthalocyanine chloride was dissolved in 50 ml of sulfuric acid and stirred at room temperature for 30 minutes, and this was added to 1 liter of ion-exchanged water cooled with ice water.
The solution was dropped in about 40 minutes and reprecipitated. Further, the mixture was stirred under cooling for 1 hour and then left overnight. After removing the supernatant liquid by decantation, the precipitate was separated by centrifugation to obtain 700 mg of precipitate. As the first washing, 120 ml of ion-exchanged water as washing water was added to 700 mg of the precipitate and stirred, and then the precipitate and the washing water were separated and removed by centrifugation.
The same washing operation was performed 5 times in succession. The pH and conductivity of the wash water separated and removed in the sixth operation (that is, the wash water after washing) were measured (23 ° C.). Model PH51 manufactured by Yokogawa Electric Corporation was used for the measurement of pH. Further, the conductivity is measured by model SC-17 manufactured by Shibata Scientific Instruments Co., Ltd.
A was used. The pH of the wash water is 3.3 and the conductivity is
It was 65.1 μS / cm. Then, it was washed 3 times with 60 ml of methanol and dried under vacuum at 60 ° C. for 4 hours. The X-ray diffraction spectrum of this dried product is shown in FIG. Next, to 1.0 g of this vacuum dried product, 9.0 g of ion-exchanged water and 86 g of toluene were added, and the mixture was heated and stirred at 60 ° C. for 8 hours, centrifuged to remove the supernatant liquid, and washed with methanol to obtain 6
It was vacuum dried at 0 ° C. for 4 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of this crystal is shown in FIG.

Production Example 2 To 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1, 9.0 g of ion-exchanged water and 86.0 g of xylene were added,
The mixture was heated and stirred at 60 ° C. for 8 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of this crystal is shown in FIG.

Production Example 3 To 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1, 9.0 g of ion-exchanged water and 87.0 g of benzene were added,
The mixture was heated and stirred at 60 ° C. for 8 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Production Example 4 To 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1, 9.0 g of ion-exchanged water and 86.0 g of toluene were added,
2 at room temperature with 1 mmφ zirconia beads in a glass bottle
Ball mill milling was performed for 0 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Production Example 5 10 g of ion-exchanged water and 86.0 g of toluene were added to 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1, and the mixture was heated and stirred at 60 ° C. for 8 hours to give the phthalocyanine of the present invention. Crystals of the composition were obtained. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Production Example 6 To 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1, 1.0 g of ion-exchanged water and 86.0 g of toluene were added,
The mixture was heated and stirred at 60 ° C. for 8 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Production Example 7 9.0 g of ion-exchanged water and 8.6 g of toluene were added to 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 6 to obtain 6
The mixture was heated and stirred at 0 ° C. for 8 hours to obtain crystals of the phthalocyanine composition of the present invention. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Production Example 8 10 g of ion-exchanged water and 1.7 g of toluene were added to 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1, and the mixture was heated and stirred at 60 ° C. for 8 hours to give the phthalocyanine of the present invention. Crystals of the composition were obtained. The X-ray diffraction spectrum of the obtained composition was the same as in FIG.

Comparative Production Example 1 To 1.0 g of the vacuum dried product obtained in the same manner as in Production Example 1 was added 86.0 g of toluene, and the mixture was heated and stirred at 100 ° C. for 1 hour to produce crystals of a phthalocyanine composition. The obtained crystal X-ray diffraction spectrum is shown in FIG.

Comparative Production Example 2 Crystals of a phthalocyanine composition were produced in the same manner as in Production Example 1 except that the phthalocyanine composition showing the X-ray diffraction spectrum of FIG. 5 was used in place of the vacuum dried product of FIG. The X-ray diffraction spectrum of the obtained crystal is shown in FIG.

Production Examples 9 to 16 Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 8 except that indium phthalocyanine bromide was used in place of indium phthalocyanine chloride in Production Examples 1 to 8.

Comparative Production Examples 3 and 4 Crystals of a phthalocyanine composition were obtained according to Comparative Production Examples 1 and 2 except that indium phthalocyanine bromide was used instead of indium phthalocyanine chloride in Comparative Production Examples 1 and 2.

Production Examples 17 to 24 Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 8 except that gallium phthalocyanine chloride was used instead of indium phthalocyanine chloride in Production Examples 1 to 8.

Comparative Production Examples 5 and 6 Crystals of phthalocyanine composition were obtained according to Comparative Production Examples 1 and 2 except that gallium phthalocyanine chloride was used instead of indium phthalocyanine chloride in Comparative Production Examples 1 and 2.

Production Examples 25 to 32 Crystals of a phthalocyanine composition were obtained according to Production Examples 1 to 8 except that aluminum phthalocyanine chloride was used instead of indium phthalocyanine chloride in Production Examples 1 to 8.

Comparative Production Examples 7 and 8 Crystals of a phthalocyanine composition were obtained according to Comparative Production Examples 1 and 2 except that aluminum phthalocyanine chloride was used instead of indium phthalocyanine chloride in Comparative Production Examples 1 and 2.

Example 1 1.5 g of the phthalocyanine composition produced in Production Example 1, 0.9 g of polyvinyl butyral resin S-REC BL-S (manufactured by Sekisui Chemical Co., Ltd.), melamine resin ML351W (manufactured by Hitachi Chemical Co., Ltd.) 0 0.1 g, 2-ethoxyethanol 49.0
g and tetrahydrofuran 49.0 g were mixed and dispersed by a ball mill. An aluminum plate (conductive substrate 100 mm x 100 mm x 0.1 mm) obtained by dipping the obtained dispersion liquid
Coated on top and dried at 140 ° C for 1 hour to a thickness of 0.5 μm
The charge generation layer of was formed. Further, the dispersion liquid was applied onto a glass plate and the absorption spectrum was measured. The results are shown in FIG. 7. The absorption spectrum was measured by Hitachi U-3410 type self-recording spectrophotometer. The above No. No. 4, charge-transporting substance 1.5 g, polycarbonate resin Iupilon S-
A coating liquid obtained by mixing 1.5 g of 3000 (manufactured by Mitsubishi Gas Chemical Co., Inc.) and 15.5 g of methylene chloride was applied on the above aluminum substrate by a dipping method, dried at 120 ° C. for 1 hour, and had a thickness of 20 μm. Was formed on the charge transport layer. The electrophotographic characteristics (sensitivity, residual potential, dark decay rate, photoresponsiveness) were evaluated by Cynthia 30HC (manufactured by Midoriya Electric Co., Ltd.). Charge the photoreceptor to -650V with the corona charging method,
A monochromatic light of nm was exposed to a 50 mS photoconductor and various characteristics were measured. The definitions of the above properties are as follows. The sensitivity (E ₅₀ ) is the irradiation energy amount of monochromatic light of 780 nm required to halve the initial charging potential of −650 V after 0.2 seconds of exposure, and the residual potential (Vr) is 20 mJ / m of the same wavelength.
50 mS exposure of ² monochromatic light, 0.2 seconds after exposure and 0.5
It is the potential remaining on the surface of the photoconductor after a second. Dark decay rate (DD
R) is (V ₁ / V) using the initial charging potential of the photoconductor of −650 V and the surface potential V ₁ (−V) after the initial charging and left in a dark place for 1 second.
650) × 100. The photoresponsiveness (T _1/2 ) is
The time required to halve the initial charging potential of -650 V by exposing 50 mS of monochromatic light of 20 mJ / m ^{2 having} a wavelength of 780 nm (se
defined as c).

Examples 2 to 8 Electrophotographic photosensitive members were produced and evaluated in the same manner as in Example 1 except that the titanyl phthalocyanine compositions obtained in Production Examples 2 to 8 were used. The results are shown in Table 1.

Comparative Examples 1 and 2 An electrophotographic photosensitive member was produced and evaluated according to Example 1 except that the titanyl phthalocyanine composition obtained in Comparative Production Examples 1 and 2 was used in Example 1. The results are shown in Table 1. Although it seems that the sensitivity is high in appearance, the dark decay rate was not a value that can be practically used. The dispersion obtained by applying the powder obtained in Comparative Production Example 1 was applied to a glass plate and the absorption spectrum was measured. The results are shown in FIG.

Comparative Example 3 An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1 except that the dry powder before the treatment with the mixed solvent of toluene-water was used in Production Example 1, but it was charged up to −650V. I couldn't.

[0065]

[Table 1]

Examples 9 to 16 The titanyl phthalocyanine compositions obtained in Production Examples 9 to 16 in Example 1 were used, and No. 6 was used as the charge transport material. Instead of the compound of No. 4, Electrophotographic photoreceptors were manufactured and evaluated according to Examples 1 to 8 except that 2 was used.
The results are shown in Table 2.

Comparative Examples 4 and 5 The titanyl phthalocyanine compositions obtained in Comparative Production Examples 4 and 5 in Example 1 were used and No. Instead of the compound of No. 4, An electrophotographic photosensitive member was produced and evaluated according to Example 1 except that 2 was used. The results are shown in Table 2.

Comparative Example 6 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the dry powder before treatment with the mixed solvent of toluene-water was used in Production Example 9, and the evaluation was made up to −650V. I couldn't.

[0069]

[Table 2]

Examples 17 to 24 The titanyl phthalocyanine compositions obtained in Production Examples 17 to 24 in Example 1 were used and No. Instead of the compound of No. 4, Electrophotographic photoreceptors were produced and evaluated according to Examples 1 to 8 except that No. 5 was used. The results are shown in Table 3.

Comparative Examples 7 and 8 In Example 1, the titanyl phthalocyanine compositions obtained in Comparative Production Examples 7 and 8 were used and No. Instead of the compound of No. 4, An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that 5 was used. The results are shown in Table 3.

Comparative Example 9 An electrophotographic photosensitive member was manufactured and evaluated in the same manner as in Example 1 except that the dry powder before the treatment with the mixed solvent of toluene-water was used in Preparation Example 17, and was charged up to -650V. I couldn't.

[0073]

[Table 3]

Examples 25 to 32 The titanyl phthalocyanine compositions obtained in Production Examples 25 to 32 in Example 1 were used and No. Instead of the compound of No. 4, An electrophotographic photosensitive member was manufactured and evaluated according to Examples 1 to 8 except that 1 was used. The results are shown in Table 4.

Comparative Examples 10 and 11 In Example 1, the titanyl phthalocyanine compositions obtained in Comparative Production Examples 10 and 11 were used, and No. 1 was used as the charge transport material. Instead of the compound of No. 4, An electrophotographic photosensitive member was manufactured and evaluated according to Example 1 except that 1 was used. The results are shown in Table 4.

Comparative Example 12 An electrophotographic photosensitive member was produced and evaluated in the same manner as in Example 1 except that the dry powder before treatment with the mixed solvent of toluene-water was used in Production Example 25. I couldn't.

[0077]

[Table 4]

[0078]

The electrophotographic photoreceptor using the phthalocyanine composition of the present invention is excellent in electrophotographic characteristics such as chargeability, dark decay and sensitivity, and is required to have higher density and higher image quality than ever before. It can be suitably applied to an electrophotographic process.

[Brief description of drawings]

FIG. 1 is an X-ray diffraction spectrum of a vacuum dried product obtained in Production Example 1.

2 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Production Example 1. FIG.

FIG. 3 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Production Example 2.

FIG. 4 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Comparative Production Example 1.

5 is an X-ray diffraction spectrum of the vacuum dried product used in Comparative Production Example 2. FIG.

6 is an X-ray diffraction spectrum of the phthalocyanine composition obtained in Comparative Production Example 2. FIG.

7 is an absorption spectrum of the dispersion liquid obtained in Example 1. FIG.

8 is an absorption spectrum of the dispersion liquid obtained in Comparative Example 1. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mikio Itagaki 4-13-1, Higashimachi, Hitachi-shi, Ibaraki Hitachi Chemical Co., Ltd. Ibaraki Research Institute

Claims (7)

[Claims] 1. A phthalocyanine composition having major diffraction peaks at Bragg angles (2θ ± 0.2 degrees) of 7.5 degrees, 24.2 degrees and 27.3 degrees in an X-ray diffraction spectrum of CuKα. 2. A phthalocyanine mixture containing a titanyl phthalocyanine and a halogenated metal phthalocyanine whose central metal is trivalent is precipitated in water by an acid pasting method, and the Bragg angle (2θ ± 0.2 degrees in the X-ray diffraction spectrum of CuKα is determined. ) An X-ray diffraction spectrum of CuKα, characterized in that a precipitate having a characteristic diffraction peak at 27.2 degrees is obtained, and the precipitate is subsequently treated with a mixed solvent of an aromatic organic solvent and water. At Bragg angle (2θ ± 0.2 degrees) of 7.5 degrees, 24.2 degrees and 2
A method for producing a phthalocyanine composition having a main diffraction peak at 7.3 degrees. 3. The method for producing a phthalocyanine composition according to claim 2, wherein the mixing ratio of the aromatic organic solvent and water is aromatic organic solvent / water = 1/99 to 99/1. 4. An electrophotographic photoreceptor having a photoconductive layer containing an organic photoconductive substance on a conductive substrate, wherein the organic photoconductive substance has a Bragg angle (2θ ± 0 in the X-ray diffraction spectrum of CuKα. 2 degrees) 7.5 degrees, 24.2
An electrophotographic photosensitive member which is a phthalocyanine composition having a main diffraction peak at 27.3 degrees and 27.3 degrees. 5. The phthalocyanine composition has an absorption spectrum in which the absorbance at 800 to 830 nm is 620 to 820.
The electrophotographic photosensitive member according to claim 4, which has an absorbance higher than 660 nm. 6. A charge generation layer containing the phthalocyanine composition according to claim 1 as a charge generation material, and a compound represented by the following general formula [I]: (R ₁ and R ₂ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a fluoroalkyl group or a fluoroalkoxy group, and two R ₃ are each independently a hydrogen atom. Or an alkyl group, Ar ₁ and Ar ₂ each independently represent an aryl group, and p, q, r and s each independently represent an integer of 0 to 5). A composite type electrophotographic photoreceptor having a charge transporting layer which is contained as a charge transporting substance. 7. A charge generating layer coating liquid containing the phthalocyanine composition according to claim 1.